Abstract

The simple organometallic, (μ-S 2 )Fe 2 (CO) 6 , serves as a precursor to synthetic analogues of the chemically rudimentary iron-only hydrogenase enzyme active site. The fundamental properties of the (μ-SCH 2 CH 2 CH 2 S)[Fe(CO) 3 ] 2 compound, including structural mobility and regioselectivity in cyanide/carbon monoxide substitution reactions, relate to the enzyme active site in the form of transition-state structures along reaction paths rather than ground-state structures. Even in the absence of protein-based active-site organization, the ground-state structural model complexes are shown to serve as hydrogenase enzyme reaction models, H 2 uptake and H 2 production, with the input of photo- or electrochemical energy, respectively.

Keywords

Active siteHydrogenaseChemistryEnzymeRegioselectivityElectrochemistryStereochemistryCatalysisCrystallographyOrganic chemistryPhysical chemistryElectrode

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Publication Info

Year
2003
Type
article
Volume
100
Issue
7
Pages
3683-3688
Citations
275
Access
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Marcetta Y. Darensbourg, Erica J. Lyon, Xuan Zhao et al. (2003). The organometallic active site of [Fe]hydrogenase: Models and entatic states. Proceedings of the National Academy of Sciences , 100 (7) , 3683-3688. https://doi.org/10.1073/pnas.0536955100

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DOI
10.1073/pnas.0536955100